A H-2-NO fuel cell was designed for the synthesis of hydroxylamine in the gas phase. The hydroxylamine produced was trapped in an aqueous solution of H2SO4 held in a silica-wool disk used as an electrolyte barrier for H-2 and NO. Among the cathode electrocatalysts tested, iron-phthalocyanine (Fe-Pc) impregnated in graphite was the most favorable one for selective synthesis of hydroxylamine. Active carbon and carbon whiskers used to support the Fe-Pc enhanced the formation of hydroxylamine remarkably. The carbon itself slightly catalyzed the formation of N2O and NH2. Excluding the effects of the support, Fe-PC catalyzed the electrochemical synthesis of hydroxylamine with high selectivity (equivalent to 100%). Applied voltage across the cell did not appreciably enhance the formation of hydroxylamine. The reaction under short-circuit conditions was most favorable for the synthesis of hydroxylamine. It is suggested that the reduction of NO occurs on the Fe-2+ site of Fe-Pc with protons and electrons transferred from the anode. The very selective synthesis of hydroxylamine over Fe-Pc must be ascribed to an Fe-2+ site isolated by phthalocyanine ring. This isolation prohibits both the formation of N2O through the intramolecular elimination of H2O from the adjacent NHO intermediates and the formation of N-2 and NH2 through the breaking of N-O bonds.